Multilayered ion exchange membranes

ABSTRACT

An ion exchange membrane has multiple layers of ionic polymers which each contain substantially different chemical compositions. i.e. varying side chain lengths, varying backbone chemistries or varying ionic functionality. Utilizing completely different chemistries has utility in many applications such as fuel cells where for example, one layer can help reduce fuel crossover through the membrane. Or one layer can impart substantial hydrophobicity to the electrode formulation. Or one layer can selectively diffuse a reactant while excluding others. Also, one chemistry may allow for impartation of significant mechanical properties or chemical resistance to another more ionically conductive ionomer. The ion exchange membrane may include at least two layers with substantially different chemical properties.

CROSS REFERENCE TO RELATED APPLICATIONS

The application is a continuation U.S. patent application Ser. No.16/560,876, filed on Sep. 4, 2019, now U.S. patent Ser. No. 11/103,864,which claims the benefit of priority to U.S. provisional patentapplication No. 62/765,537, filed on Sep. 4, 2018; the entirety of whichis hereby incorporated by reference herein.

BACKGROUND OF THE INVENTION

The invention relates to solid polymer ion exchange membranes suitablefor use in electrochemical and pervaporative applications.

BACKGROUND

Ion exchange membranes (IEM) are used in electrochemical devices assolid electrolytes. A membrane separating the cathode and anodetransports ions formed at the catalyst layer of one electrode to theother electrode, enabling the device to function by either providing anelectrical current (in the case of a fuel cell), producing gases (in thecase of an electrolyzer), or compressing a gas (in the case of anelectrochemical compressor).

For fuel cells, solid polymer electrolyte electrolyzers andelectrochemical compressors to achieve full commercialization andwidespread integration, they must achieve high power densities at lowcosts. To do so, high performance IEMs are required. High performanceIEMs can be characterized by high ion conductivity, low electricalconductivity, low gas permeance (commonly referred to as crossover),high mechanical strength, and high dimensional stability.

To achieve these properties, numerous strategies have been examined.U.S. Pat. No. 5,547,551 to Bahar et al. describes a composite IEMprepared by impregnating a porous material, in this case an expandedpolytetrafluoroethylene membrane with thickness less than 0.025 mm, withan ion exchange material, in this case perfluorosulfonic acid (PFSA).This form of IEM has become the preferred form of IEM for automotivefuel cell applications, enabling high ion conductance and highmechanical strength and stability at a low thickness. Typical examplesof composite ion exchange membranes reinforced with porous materials areGORE-SELECT sold by W. L. Gore and Associates, Nafion® XL sold byChemours, and Tokuyama A201 from Tokuyama Corp.

A critical issue with thin IEMs is fuel (in the case of a hydrogen fuelcell, hydrogen) crossover across the membrane during operation.Crossover results in both degradation of the membrane and reduced fuelcell performance. Crossover in an electrochemical cell is oftencharacterized by electrochemical techniques and is described as acrossover current density.

In proton exchange membrane (PEM) fuel cells (PEMFC), reinforcedcomposite PFSA membranes are the preferred form for leading automotivefuel cell applications. PFSA polymers are produced by several companiesunder several brand names, such as Nation® from Chemours, Flemion® fromAsahi Glass Co. Chemicals, Aquivion® from Solvay Specialty Polymers, andDyneon™ from 3M. Some key differences among various PFSA polymers aretheir ion exchange capacities or degree of sulfonic acidfunctionalization, which is often expressed as equivalent weight (EW) ing/mol, and their side chain lengths, which can be expressed as thenumber of carbon atoms in the side chain.

PFSA equivalent weights are expressed in grams of polymer per moles ofsulfonic acid functional groups. Generally, PFSA water uptake by mass,swelling by volume, and conductivity increase with decreasing equivalentweight.

PFSA side chain lengths are often described qualitatively, in thatpolymers are referred to as “long side chain” or “short side chain.”Nation® ion exchange polymers are referred to as “long side chain,”having six carbons in their side chains with two vinyl ether groups,while Aquivion ion exchange polymers are referred to as “short sidechain,” having two carbons in their side chains and one vinyl ethergroup. Short side chain polymers exhibit higher degrees ofcrystallinity, lower hydrogen crossover, and lower water uptake behaviorat the same EW relative to long side chain polymers.

It has been demonstrated that short side chain PFSA polymers exhibitsignificantly lower hydrogen crossover, as characterized by currentdensity, than their long side chain counterparts. Additionally, shortside chain PFSA polymers demonstrate greater stability of hydrogencrossover over several days at OCV conditions.

In the case of non-PFSA ion exchange polymers, especially in the case ofanion exchange polymers, various cationic functional groups grafted tothe same polymer backbone can exhibit various degrees of fuel crossoverand conductivity. For example, an anion exchange polymer may contain atetramethylammonium functional group to provide anion exchange capacity.However, substitution of this functional group with a pyridinium orpiperidinium functional group may result in varying fuel crossover orconductivity properties.

U.S. Pat. No. 6,130,175A to Rusch et al. describes a multi-layeredcomposite ion exchange membrane suitable for use in fuel cells orelectrodialysis applications. The multi-layers described haveessentially the same chemistry (i.e. backbone and functional groups) butsimply different densities of functional groups from one layer to thenext. The patent does not cover use of substantially differentchemistries employed such as an ionomer with a different polymer sidechains or for example combining cationic with anionic polymers or theuse of anion exchange chemistries with different backbone chemistriesdescribed herein within any layer.

Chemours Nafion products markets a membrane product to the chlor-alkaliindustry made with perfluorinated sulfonic acid ionomer, with thin layerof a similar perfluorinated carboxylic acid functionalize ionomer.Substituting the sulfonic acid group with carboxylic acid, however,maintaining the chemistry of the backbone structure. Again, the ionomerchemistries are substantially the same.

Again, in this invention, the overall membrane consists of at least twolayers with substantially different chemical properties, wherein atleast one layer is a composite membrane.

SUMMARY OF THE INVENTION

The present invention describes an ion exchange membrane comprisingmultiple layers of ionic polymers which each contain substantiallydifferent chemical compositions, i.e. varying side chain lengths,varying backbone chemistries or varying ionic functionality.

Utilizing completely different chemistries has utility in manyapplications such as fuel cells where for example one layer can helpreduce fuel crossover through the membrane. Or one layer can impartsubstantial hydrophobicity to the electrode formulation. Or one layercan selectively diffuse a reactant while excluding others. Also, onechemistry may allow for impartation of significant mechanical propertiesor chemical resistance to another more ionically conductive ionomer.

In this invention, the overall membrane composite comprises at least twolayers with substantially different chemical properties.

In one aspect, the present invention provides an ion exchange membranecomprising a porous reinforcement scaffold imbibed with multiple layersof variously functionalized ionic polymers. Typically, the membrane is50 microns or less, more typically 30 microns or less and in someembodiments 20 microns or less.

In one embodiment, a membrane is prepared by providing two distinctsolutions of PFSA polymers of various equivalent weights in mixtures ofwater and alcohols along with a porous reinforcement material. Theporous reinforcement material is coated on one side with the firstsolution with a doctor blade and then dried. Then, the porousreinforcement material is coated on the second side with the secondsolution and then dried, filling the remainder of the pores in thereinforcement material and creating a multilayer ion exchange membrane.

The ion conducting polymers including a PFSA polymers may havesubstantially different equivalent weights, such as at least about 20%different, or at least about 30% different, or as high as 40% different,or at least 50% different such as a 1500 versus 900 equivalent weightfor example. Likewise, the ion conducting polymers may havesubstantially different side chain lengths such as such as at leastabout 20% different, or at least about 30% different, or as high as 40%different, or at least 50% different and any range between and includingthe percentages listed.

The summary of the invention is provided as a general introduction tosome of the embodiments of the invention, and is not intended to belimiting. Additional example embodiments including variations andalternative configurations of the invention are provided herein.

BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWINGS

The accompanying drawings are included to provide a furtherunderstanding of the invention and are incorporated in and constitute apart of this specification, illustrate embodiments of the invention, andtogether with the description serve to explain the principles of theinvention.

FIG. 1 and FIG. 2 show common perfluorosulfonic acid (PFSA) chemicalstructures.

FIG. 3 , FIG. 4 , and FIG. 5 show several possible quaternary ammoniumcationic functional groups.

FIG. 6 shows an exemplary porous reinforcement scaffold material.

FIG. 7 shows an example of a membrane with two different equivalentweight ion exchange polymers.

FIG. 8 . shows an example of a membrane with two different side chainlengths.

FIG. 9 . shows an example of a membrane with two different functionalgroups.

Corresponding reference characters indicate corresponding partsthroughout the several views of the figures. The figures represent anillustration of some of the embodiments of the present invention and arenot to be construed as limiting the scope of the invention in anymanner. Further, the figures are not necessarily to scale, some featuresmay be exaggerated to show details of particular components. Therefore,specific structural and functional details disclosed herein are not tobe interpreted as limiting, but merely as a representative basis forteaching one skilled in the art to variously employ the presentinvention.

DETAILED DESCRIPTION OF THE ILLUSTRATED EMBODIMENTS

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a process,method, article, or apparatus that comprises a list of elements is notnecessarily limited to only those elements but may include otherelements not expressly listed or inherent to such process, method,article, or apparatus. Also, use of “a” or “an” are employed to describeelements and components described herein. This is done merely forconvenience and to give a general sense of the scope of the invention.This description should be read to include one or at least one and thesingular also includes the plural unless it is obvious that it is meantotherwise.

Certain exemplary embodiments of the present invention are describedherein and are illustrated in the accompanying figures. The embodimentsdescribed are only for purposes of illustrating the present inventionand should not be interpreted as limiting the scope of the invention.Other embodiments of the invention, and certain modifications,combinations and improvements of the described embodiments, will occurto those skilled in the art and all such alternate embodiments,combinations, modifications, improvements are within the scope of thepresent invention.

In one embodiment, a membrane is prepared by providing two distinctsolutions of PFSA polymers of various equivalent weights in mixtures ofwater and alcohols along with a porous reinforcement material. Theporous reinforcement material is coated on one side with the firstsolution with a doctor blade and then dried. Then, the porousreinforcement material is coated on the second side with the secondsolution and then dried, filling the remainder of the pores in thereinforcement material and creating a multilayer ion exchange membrane.The ion conducting polymers including a PFSA polymers may have differentequivalent weights, such as at least about 0% different, or at leastabout 30% different, or as high as 40% different, or at least 50%different such as a 1500 versus 900 equivalent weight for example.Likewise, the ion conducting polymers may have varying side chainlengths such as such as at least about 20% different, or at least about30% different, or as high as 40% different, or at least 50% differentand any range between and including the percentages listed.

FIG. 1 and FIG. 2 show two examples of exemplary PFSA structures. FIG.1A is a representation of a “long side chain” PFSA polymer, whichcontains five carbons in the side chain, while FIG. 2 is arepresentation of a “short side chain” PFSA polymer, containing twocarbons in the side chain.

FIG. 3 , FIG. 4 and FIG. 5 show three examples of exemplary quaternaryammonium functional groups. FIG. 3 is a representation of atrimethylammonium functional group, FIG. 4 is a representation of apyrrolidinium functional group, and FIG. 5 is a representation of apiperidinium functional group. In all cases, “R” is standard organicchemistry notation and indicates any other group containing carbon orhydrogen, presumed here to indicate the polymer side chain.

As shown in FIG. 6 , an exemplary porous scaffold 10 has a thickness 30from a first side 20 and an opposite second side 40. The porous scaffoldhas pores 50 and an open structure extending from the first side 20 tothe second side 40, allowing for a flow of appropriate fluid from thefirst to the second side. The porous scaffold is air permeable when notimbibed with another solid material.

As shown in FIG. 7 , a multilayered membrane 100 may comprise a firstlayer 110 comprising an ion exchange polymer with a first equivalentweight 60 and a second layer 120 comprising an ion exchange polymer witha second equivalent weight 70, both imbibed into the porous scaffold 10.

As shown in FIG. 8 , a multilayered membrane 130 may comprise a firstlayer 140 comprising an ion exchange polymer with a first side chainlength 80 and a second layer 150 comprising an ion exchange polymer witha second side chain length 90, both imbibed into the porous scaffold 10.

As shown in FIG. 9 , a multilayered membrane 160 may comprise a firstlayer 170 comprising an ion exchange polymer with a functional group 200and a second layer 180 comprising an ion exchange polymer with a secondfunctional group 210, both imbibed into the porous scaffold 10.

It will be apparent to those skilled in the art that variousmodifications, combinations and variations can be made in the presentinvention without departing from the scope of the invention. Specificembodiments, features and elements described herein may be modified,and/or combined in any suitable manner. Thus, it is intended that thepresent invention cover the modifications, combinations and variationsof this invention provided they come within the scope of the appendedclaims and their equivalents.

What is claimed is:
 1. A composite ion exchange membrane comprising: a)a first layer of ion exchange polymer having a first equivalent weight,a first side chain length, and a first functional group; and b) a secondlayer of ion exchange polymer having a second equivalent weight that isat least 20% greater than said first equivalent weight, whereinequivalent weight is grams of ion exchange polymer per moles offunctional groups in said ion exchange polymer.
 2. The ion exchangemembrane of claim 1, wherein the ion exchange polymer is a cationexchange polymer.
 3. The ion exchange membrane of claim 1, wherein theion exchange polymer is perfluorinated.
 4. The ion exchange membrane ofclaim 1, wherein the ion exchange polymer is perfluorosulfonic acid(PFSA).
 5. The ion exchange membrane of claim 4, wherein the first layerof ion exchange polymer has an equivalent weight of ion exchange polymerper moles of functional group of 800 g/mol or less.
 6. The ion exchangemembrane of claim 1, wherein the first functional group is a sulfonicacid functional group.
 7. The ion exchange membrane of claim 6, whereinthe second layer of ion exchange membrane has carboxylic acid functionalgroups.
 8. The ion exchange membrane of claim 1, wherein the ionexchange polymer is an anion exchange polymer.
 9. The ion exchangemembrane of claim 1, wherein the composite ion exchange membrane furthercomprises a porous scaffold material and wherein at least one of thefirst layer of ion exchange polymer or second layer of ion exchangepolymer is configured in said porous scaffold material.
 10. The ionexchange membrane of claim 9, wherein the porous scaffold material isselected from the group consisting of: microporous polyethylene,microporous polypropylene, or microporous polytetrafluoroethylene. 11.The ion exchange membrane of claim 10, wherein the porous scaffoldmaterial has a pore size of 0.005 microns to 0.05 microns.
 12. The ionexchange membrane of claim 1, wherein, the first layer of ion exchangepolymer has a first side chain length and wherein the second layer ofion exchange polymer has a second side chain length that is at least 20%longer than said first side chain length.
 13. The ion exchange membraneof claim 1, wherein the first layer of ion exchange polymer has a firstfunctional group and wherein the second layer of ion exchange polymerhas a second functional group that is different than said firstfunctional group.
 14. A composite ion exchange membrane comprising: a) afirst layer of anion exchange polymer having a first side chain length;b) a second layer of anion exchange polymer having a second side chainlength that is at least 20% longer than said first side chain length.15. The composite ion exchange membrane of claim 14, wherein a polymerbackbone of the first anion exchange polymer comprisespoly(biphenylene), poly(triphenylene), orpoly(styrene-b-ethylene-b-butadiene-b-ethylene).
 16. The ion exchangemembrane of claim 15 wherein the first layer of anion exchange polymerhas first functional groups that are located on a first side chain ofthe first anion exchange polymer and wherein said first side chain hasfour or more carbons grafted to the backbone of the first anion exchangepolymer.
 17. The ion exchange membrane of claim 15, wherein the firstlayer of anion exchange polymer has first functional groups that arelocated as part of a polymer backbone of the first anion exchangepolymer.
 18. The ion exchange membrane of claim 17, wherein the backboneof the first layer of anion exchange polymer comprisespoly(biphenylene), poly(triphenylene), orpoly(styrene-b-ethylene-b-butadiene-b-ethylene).
 19. The ion exchangemembrane of claim 14, wherein the first layer of anion exchange polymerhas trimethylammonium or piperidinium function groups.
 20. The ionexchange membrane of claim 15, wherein the second layer of anionexchange polymer has pyrrolidinium or piperidinium functional groups.